(Nitro)Iron(III) Porphyrins. EPR Detection of a Transient Low-Spin Iron(III) Complex and Structural Characterization of an O Atom Transfer Product.

The reaction of BF(3).OEt(2) with the bis(nitro) complex of iron(III) picket-fence porphyrin, [K(18C6)(OH(2))][Fe(TpivPP)(NO(2))(2)], leads to the formation of a transient porphyrin intermediate, assigned on the basis of its rhombic low-spin EPR spectrum as the five-coordinate N-bound mono(nitro) iron(III) derivative, [Fe(TpivPP)(NO(2))]. This species is reactive and readily undergoes oxygen atom transfer to form [Fe(III)(TpivPP)(NO(3))] and [Fe(II)(TpivPP)(NO)]. The reactions have been followed by EPR and IR spectroscopy. [Fe(TpivPP)(NO(2))] has a rhombic EPR spectrum (g = 2.60, 2.35, and 1.75) in chlorobenzene and CH(2)Cl(2) and is spectroscopically distinct from the bis(nitro) starting material (g = 2.70, 2.50, and 1.57). Oxidation of the nitrosyl species to [Fe(TpivPP)(NO(3))] proceeds via an intermediate assigned as [Fe(TpivPP)(NO(2))] on the basis of its EPR spectrum. The crystal structure of one of the reaction products, [Fe(TpivPP)(NO(3))], has been determined. The nitrate ion of [Fe(TpivPP)(NO(3))] is bound to the iron(III) ion in a "symmetric" bidentate fashion within the ligand-binding pocket of the porphyrin pickets. Individual Fe-O distances are 2.123(3) and 2.226(3) Å. The dihedral angle between the plane of the nitrate ion and the closest N(p)-Fe-N(p) plane is 10.0 degrees. The Fe-N(p) bonds (and trans N(p)-Fe-N(p) angles) perpendicular and parallel to the plane of the axial ligand average to 2.060(5) Å (154.84(9) degrees ) and 2.083(3) Å (146.14(9) degrees ), respectively. Crystal data for [Fe(TpivPP)(NO(3))]: a = 23.530(2) Å, b = 10.0822(5) Å, c = 48.748(3) Å, beta = 92.145(5) degrees, monoclinic, space group I2/a, V = 11556.4(14) Å(3), Z = 8, FeN(9)O(7)C(64)H(64), 8798 observed data, R(1) = 0.0606, wR(2) = 0.1313, all observations at 127(2) K.